Imide functional polyphenols; thermosettable compositions containing same and cured products therefrom

ABSTRACT

Imide functional polyphenols are prepared by reacting an excess of a phenol with an unsaturated diimide which is prepared by reacting an unsaturated polycycloaliphatic dicarboxylic acid anhydride with a diamine. These materials are useful in the preparation of castings, coatings, laminates and the like.

This is a divisional of application Ser. No. 679,529, filed Dec. 7, 1984now U.S. Pat. No. 4,555,563.

BACKGROUND OF THE INVENTION

The present invention pertains to new compositions of matter, to novelthermosettable compositions containing them and to cured productstherefrom.

Thermosettable compositions such as polycyanates and polyepoxides arewell known. Typical of these compositions are bisphenol A dicyanate andthe diglycidyl ether of bisphenol A. Such compositions are useful in thepreparation of castings, laminates, coatings and the like, with manydesirable properties. However, there is room for improvement in themechanical properties and physical properties, such as moistureresistance, of said castings, laminates, coatings, and the like.

The present invention provides a class of novel imide functionalpolyphenols as well as thermosettable polycyanates and polyepoxidesthereof. The thermoset (cured) resins have an improvement in one or moreproperties such as hardness, flexural strength, flexural modulus,resistance to moisture, and the like.

SUMMARY OF THE INVENTION

The present invention is directed to new compositions of matterrepresented by the formulas: ##STR1## wherein each Q is independently##STR2## each R is independently a hydrocarbyl group having from 1 toabout 10, preferably from 2 to about 5 carbon atoms or a ##STR3## group;each A is independently a divalent hydrocarbyl group having from 1 toabout 10, preferably from about 1 to about 4 carbon atoms, --S--,--S--S--, --O--, ##STR4## each R' is independently hydrogen, chlorine,bromine, a hydrocarbyl or hydrocarbyloxy group having from 1 to about 3carbon atoms; each R" is hydrogen or a hydrocarbyl group having from 1to about 3 carbon atoms; Z is independently hydrogen or a grouprepresented by the formulas ##STR5## or --C.tbd.N; each x has a value ofzero or 1; each y has a value of zero or 1; each n independently has anaverage value from zero to about 20, preferably from zero to about 8,and n¹ has a value from zero to about 10, preferably from zero to about2.

The major component (about 75 to 100 percent) of these compositions isrepresented by Formula I where n¹ has a value of zero, while minorcomponents (0 to about 25 percent) are represented by Formulas I and IIwhere n¹ has a value from 1 to about 10. All of the compositionsrepresented by Formulas I and II are isomeric mixtures wherein thesubstitution of the phenolic (or substituted phenoxy) groups by thenorbornyl group is in the ortho and para positions.

The present invention also concerns thermosettable (curable)compositions of the compositions represented by Formulas I or II whereineach Z is a ##STR6## or --C.tbd.N group.

The present invention also concerns polyepoxide compositions which arethermosettable upon curing with a curing quantity of a suitable curingagent. Said polyepoxide compositions are prepared by advancementreaction (copolymerization) of the compositions represented by FormulasI or II wherein each Z is hydrogen, with a polyepoxide of Formulas III,IV, V, VI or a mixture thereof ##STR7## wherein each R', R", y and A areas hereinbefore defined; each A' is independently a divalent hydrocarbylgroup having from 1 to about 10, preferably from 1 to about 4 carbonatoms; m has a value of from zero to about 40, preferably from zero toabout 10; and m' has a value of from about 0.001 to about 10, preferablyfrom about 0.01 to about 3.

The present invention also concerns polyepoxide compositions prepared byreacting a composition represented by Formulas I or II wherein each Z is##STR8## with a phenolic material represented by Formulas VII, VIII, IX,X or a mixture thereof. ##STR9## wherein each A, A', R', m' and y are ashereinbefore defined.

The present invention also concerns polyepoxide compositions prepared byreacting a composition represented by Formulas I or II wherein each Z isa ##STR10## group with a material represented by Formulas I or II or amixture thereof wherein each Z is a hydrogen.

The present invention also concerns cured and curable compositionsthereof.

DETAILED DESCRIPTION OF THE INVENTION

The imide functional polyphenols can be prepared by the reaction of astoichiometric excess of a phenol of the structure represented byFormula XI with an unsaturated diimide of the structure represented byFormula XII in the presence of an acidic catalyst. ##STR11## whereineach R, R', x and n are as hereinbefore defined, and with the provisothat at least one ortho or para R' in formula XI is a hydrogen.

The unsaturated diimide represented by Formula XII is obtained bycondensation reaction of an unsaturated polycycloaliphatic dicarboxylicacid anhydride of the structure represented by Formula XIII with adiamine of the structure represented by Formula XIV, XV or a mixturethereof. ##STR12## wherein each A, R, R', y, x and n are as hereinbeforedefined.

In the compositions represented by Formulas I and II when n is zero andx is 1, the unsaturated polycycloaliphatic dicarboxylic acid anhydriderepresented by Formula XIII is endomethylenetetrahydrophthalic anhydride(carbic anhydride). In the compositions represented by Formulas I and IIwhen n is zero and x is zero, the unsaturated polycycloaliphaticdicarboxylic acid anhydride represented by Formula XIII istetrahydrophthalic anhydride. In the compositions represented byFormulas I and II when n has a value of 1 to about 20, the unsaturatedpolycycloaliphatic dicarboxylic acid anhydride represented by FormulaXIII is a Diels-Alder adduct of an unsaturated dicarboxylic acidanhydride and a diolefin. As a specific example, reaction of a 10 to 1mole ratio of cyclopentadiene with maleic anhydride provides anunsaturated polycycloaliphatic dicarboxylic acid anhydride representedby Formula XIII wherein n has a value of 1 to about 10 and x is 1.

The imide functional polyphenols are prepared by reacting a phenolrepresented by Formula XI and an unsaturated diimide represented byFormula XII at a reaction temperature of from about 75° C. to about 175°C. with reaction temperatures of 100° C. to 155° C. being preferred. Ifdesired, inert solvents such as xylene can be employed. Typical acidiccatalysts include boron trifluoride etherate, acid ion exchange resins,and Filtrol 1 (an acidified clay manufactured by Filtrol Corporation).

The imide functional polyphenols wherein the compositions represented byFormula I (Z is hydrogen) are present at 95 percent or more require theuse of a mole ratio of phenol (Formula XI) to unsaturated diimide(Formula XII) of about 10 to 1, preferably about 15 to 1. The imidefunctional polyphenols wherein the compositions represented by FormulaII are present at 5 to about 20 percent or more require the use of amole ratio of phenol (Formula XI) to unsaturated diimide (Formula XI) ofless than 10 to 1, preferably about 8 to 1 to about 4 to 1. At moleratios below 8 to 1, unreacted unsaturated diimide (Formula XII) alsoremains in the product.

Excess (unreacted) phenol may be removed from the imide functionalpolyphenols by vacuum distillation, azeotropic distillation, extractionor a combination of these methods. Because of its ease of removal,phenol, per se, is a most preferred reactant as represented by FormulaXI.

The polyepoxide compositions of the imide functional polyphenols arerepresented by Formulas I and II wherein Z is ##STR13## Saidcompositions are prepared using epoxidation methods described inHandbook of Epoxy Resins by Lee and Neville, McGraw-Hill, 1967 which isincorporated herein by reference. This usually includes reacting theimide functional polyphenol (Formulas I or II where Z is hydrogen) withan epihalohydrin followed by dehydrohalogenation with a basic-actingmaterial such as an alkali metal hydroxide and finally recovering theresultant glycidyl ether product.

Suitable curing agents and/or catalysts for the polyepoxide compositionsare described in the aforementioned Handbook of Epoxy Resins.

The polyepoxide compositions of the imide functional polyphenols(Formulas I or II where Z is a ##STR14## group) can be mixed with 1 to99 percent by weight (pbw), preferably 40 to 80 pbw of a polyepoxidecomposition (Formulas III, IV, V, VI or a mixture thereof) and thencured as previously described.

The polycyanate compositions of the imide functional polyphenols arerepresented by Formulas I and II where Z is a --C.tbd.N group. Saidcompositions are prepared by reaction of an imide functional polyphenol(Formulas I or II where Z is hydrogen) with a cyanogen halide in thepresence of a suitable base.

Suitable cyanogen halides which can be employed herein include, forexample, cyanogen chloride, cyanogen bromide, mixtures thereof and thelike.

If desired, the method reported in Organic Syntheses, Vol. 61, pages35-37 (1983), published by John Wiley and Sons, may be used to generatethe required amount of cyanogen halide in situ, although this is lesspreferred than using neat cyanogen halide.

Suitable base materials which can be employed herein include bothinorganic bases and tertiary amines, such as, for example, sodiumhydroxide, potassium hydroxide, triethylamine, mixtures thereof and thelike. The tertiary amines are most preferred as the base material.

The reaction is usually conducted at a temperature of from about -40° C.to about 60° C., preferably from -20° C. to about 25° C. for from about10 minutes (600 s) to about 120 minutes (7200 s), preferably from about10 minutes (600 s) to about 60 minutes (3600 s).

The reaction is preferably conducted in the presence of an inert solventreaction medium. Suitable such solvents include, for example, water,chlorinated hydrocarbons, ketones, mixtures thereof and the like.Acetone or methylene chloride are most preferred as the inert solventreaction medium.

A mole ratio of from about 1.2 to 1.0, preferably 1.1 to 1.0 cyanogenhalide per phenolic hydroxyl group is employed. A mole ratio of fromabout 1.2 to 1.0, preferably 1.05 to 1.0 of the base material perphenolic hydroxyl group is employed.

The polycyanate compositions of the imide functional polyphenolsrepresented by Formulas I and II where Z is a --C.tbd.N group arethermoset (cured) using a curing quantity of a suitable curing agent toprovide polymers containing the triazine group. Suitable curing agentswhich can be employed herein include, for example, metal salts ofcarboxylic acids, such as, lead octoate, zinc stearate, zincacetylacetonate, at concentrations of about 0.001 to 5 percent byweight. Most preferred catalysts are cobalt naphthenate and cobaltoctoate, mixtures thereof and the like. Curing is usually conducted at atemperature of from about 70° C. to about 350° C., preferably from about70° C. to about 200° C. for a period of from about 15 minutes (900 s) toabout 120 minutes (7200 s), preferably from about 30 minutes (1800 s) toabout 75 minutes (4500 s). The polycyanate compositions of the imidefunctional polyphenols also may be cured without the use of a curingagent, however, longer times and higher temperatures are typicallyrequired.

The polycyanate compositions of the imide functional polyphenols(Formulas I and II wherein Z is a --C.tbd.N group) can be mixed with 1to 99 pbw, preferably 50 to 90 pbw of a polycyanate compositionrepresented by Formulas XVI, XVII, XVIII, XIX or a mixture thereof##STR15## wherein R', A, A', y and m' are as hereinbefore defined and phas a value of zero to about 100, preferably from zero to about 10.Curing of the polycyanate mixture is accomplished as previouslydescribed.

The polycyanate compositions of the imide functional polyphenols(Formulas I and II wherein Z is a --C.tbd.N group) can be mixed with apolyepoxide composition (Formulas III, IV, V, VI or a mixture thereof)and the mixture then cured using the methods previously described forthe polycyanate compositions, per se. One or more of the polycyanatecompositions represented by Formulas XVI, XVII, XVIII or XIX may also beadded to the aforesaid polycyanate and polyepoxide mixture(s). If thepolycyanate and polyepoxide are combined stoichiometrically (a one toone mole ratio of --C.tbd.N to ##STR16## groups is provided) then curedpolymers containing the oxazoline group are provided. If the polycyanateand less than stoichiometric polyepoxide are combined then curedpolymers containing both oxazoline and triazine groups are provided.

Polyepoxide compositions are prepared, for example, by advancementreaction (copolymerization) of the imide functional polyphenols(Formulas I or II wherein each Z is hydrogen) and a polyepoxidecomposition (Formulas III, IV, V, VI or a mixture thereof) in thepresence of a suitable catalyst. Suitable catalysts which can beemployed herein include, for example, the quaternary ammonium salts,phosphonium salts, mixtures thereof and the like. A most preferredcatalyst is benzyltrimethylammonium chloride.

The advancement reaction is usually conducted at a temperature of fromabout 80° C. to about 200° C., preferably about 100° C. to about 150° C.for from about 10 minutes (600 s) to about 120 minutes (7200 s),preferably from about 30 minutes (1800 s) to about 60 minutes (3600 s).

A mole ratio of from about 0.01 to 0.99, preferably 0.05 to 0.30 ofphenolic hydroxyl group per epoxide group is used in the advancementreaction.

Curing of the polyepoxide compositions from the advancement reactions isaccomplished as previously described for the polyepoxide compositions,per se.

The cured compositions of the present invention can be used to preparecastings, laminates or composites, coatings, preimpregnated fabrics orcloths, encapsulations and the like, and are especially suited for usein environments demanding high mechanical strength and moistureresistance.

The following examples are illustrative of the invention, but are not tobe construed as to limiting the scope thereof in any manner.

EXAMPLE 1 A. Preparation of Unsaturated Diimide

A solution of 1,2-diaminoethane (49.5 grams, 0.825 mole) anddimethylformamide (300 milliliters) was heated to 60° C. with stirringand maintained under a nitrogen atmosphere.Endomethylenetetrahydrophthalic anhydride (270.0 grams, 1.65 moles) wasadded to the reactor over a 45-minute (2700 s) period after which timethe reactor was heated to 100° C. and held for 60 minutes (3600 s). Thereaction temperature was then increased to 120° C. and held for 240minutes (14400 s). After this time, no further water was being recoveredinto the Dean Stark trap-cold water condenser assembly, hence thereactor was cooled to room temperature (26° C.). The reaction productwas dissolved in hot tetrahydrofuran solvent and then allowed to standovernight. The crystalline product was removed by filtration andtwice-washed with a 50-50 percent by volume mixture of methylenechloride and methanol. The white crystals were dried under vacuum for 12hours (42300 s) at 86° C. until a constant product weight of 212.5 grams(73 percent yield) was recovered. Infra-red spectrophotometric analysisand nuclear magnetic resonance spectroscopy confirmed the productstructure for the diimide of endomethylenetetrahydrophthalic anhydride.

B. Preparation of Imide Functional Polyphenol

Phenol (285.0 grams, 3.0 moles) and boron trifluoride etherate (4.0grams) were heated to 110° C. with stirring and maintained under anitrogen atmosphere. A portion of the diimide ofendomethylenetetrahydrophthalic anhydride (70.4 grams, 0.20 mole) wasadded to the reactor and the reaction temperature was increased to 150°C. and held for 180 minutes (10800 s). After this time, the excessphenol was vacuum distilled from the reactor. The reactor was thencooled to room temperature (26° C.) then water (90 milliliters) wasadded and then removed by rotary evaporation. t-Butanol (100milliliters) was then added and phenol plus t-butanol azeotrope removedby rotary evaporation. The product was placed in a 9-inch by 6-inch flatglass tray and dried under vacuum (50 millimeters Hg) for 24 hours(86400 s) at 120° C. The polyphenol of the diimide ofendomethylenetetrahydrophthalic anhydride (109 grams, 99 percent yield)was recovered as a light yellow colored, brittle, transparent solid.Infra-red spectrophotometric analysis, nuclear magnetic resonancespectroscopy and liquid chromatographic analysis confirmed the productstructure.

C. Preparation of Polycyanate of the Imide Functional Polyphenol

Cyanogen bromide (38.14 grams, 0.3601 mole) was added to a reactorcontaining stirred chloroform (60 milliliters) under a nitrogenatmosphere. The cyanogen bromide-chloroform solution was cooled to -5°C. then a portion of the diimide polyphenol (92.0 grams, 0.1715 mole)dissolved in chloroform (282 milliliters) was added to the reactor. Thestirred solution was allowed to equilibrate at -5° C. then triethylamine(34.88 grams, 0.3447 mole) was added to the reactor over a 20-minute(1200 s) period and so as to maintain the reaction temperature at -5° to0° C. After completion of the triethylamine addition, the reactiontemperature was maintained at -1° to 6° C. for an additional 30 minutes(1800 s) followed by addition of the reaction product to chilled water(1200 milliliters) with agitation. After 5 minutes (300 s), the waterand product mixture was added to a separatory funnel and the organiclayer recovered. The organic layer was washed with 5 percenthydrochloric acid (400 milliliters), water (800 milliliters) and thendried over anhydrous sodium sulfate. The dry chloroform extract wasfiltered and solvent removed by rotary evaporation under vacuum. Thepolycyanate of the polyphenol of the diimide ofendomethylenetetrahydrophthalic anhydride was recovered as a lightyellow colored, brittle, transparent solid. Infra-red spectrophotometricanalysis and nuclear magnetic resonance spectroscopy confirmed theproduct structure.

COMPARATIVE EXPERIMENT A Preparation of Bisphenol A Dicyanate

A quantity of 222.45 grams (2.10 moles) of cyanogen bromide was added toa reactor containing 350 milliliters of stirred acetone under a nitrogenatmosphere. The cyanogen bromide-acetone solution was cooled to -5° C.,then 228.30 grams (1.0 mole) of Bisphenol A dissolved in 700 millilitersof chilled acetone was added to the reactor. The stirred solution wasallowed to equilibrate at -5° C., then 203.39 grams of triethylamine(2.01 moles) was added to the reactor over a 24-minute (1440 s) periodand so as to maintain the reaction temperature at -5° C. to 0° C. Aftercompletion of the triethylamine addition, the reactor was maintained at-11° to 1° C. for 40 minutes (2400 s), followed by addition of thereaction product to 3600 milliliters of chilled water with agitation.After 5 minutes (300 s), the water and product mixture was multiplyextracted with methylene chloride. The combined methylene chlorideextracts were sequentially washed with dilute 5 percent hydrochloricacid, water, dilute hydrochloric acid, water and then dried overanhydrous magnesium sulfate. The dry methylene chloride extract wasfiltered and solvent removed by rotary evaporation under vacuum.Bisphenol A dicyanate, 265.5 grams, was recovered in 95.4 percent yieldas a light tan colored crystalline solid. Infra-red spectrophotometricanalysis confirmed the product structure.

Prior to use, the Bisphenol A dicyanate was recrystallized from acetonethen dried in a vacuum oven to provide a white crystalline solid.

EXAMPLE 2

A pair of 12 in.×12 in. (304.8 mm×304.8 mm) woven fiberglass clothpieces were equally impregnated with a solution prepared from 10.0 gramsof the polycyanate diimide of Example 1-C, 40.0 grams of Bisphenol Adicyanate of Comparative Experiment A, 100 grams of chloroform, and0.166 gram of cobalt naphthenate (6.0 percent active). The fiberglasscloth used was a commercial-grade product treated with a proprietarycoupling agent (Burlington 76-28 electrical laminating cloth) and had anaverage weight of 0.14 gram per square inch (0.0217 g/cm²). The pair ofimpregnated fiberglass cloths were allowed to dry for 24 hours (86400 s)at room temperature (25° C.) followed by prepolymerization (B-staging)in a vented, forced-air, convection-type oven for 10 minutes (600 s) at70° C., 10 minutes (600 s) at 100° C., then 20 minutes (1200 s) at 150°C. Each cloth was cooled, found to be tack-free at room temperature andthen cut to provide eight 6 in.×6 in. (152.4 mm×152.4 mm) pieces. Thepieces were stacked into a 6 in.×6 in.×1/16 in. (152.4 mm×152.4mm×1.5875 mm) stainless steel frame and placed between stainless steelplates which had been coated with a silicone mold release. The plateswere loaded into a 177° C. hot press (Pasadena Hydraulics, Inc., ModelP-215) and maintained for two hours (7200 s) at 5000 psi (34.5 MPa).After this time a 6 in.×6 in.×1/16 in. (152.4 mm×152.4 mm×1.5875 mm)light amber-colored, semi-transparent, rigid laminate was recovered andcut to provide a set of four 1 in.×2 in.×1/16 in. (25.4 mm×50.8mm×1.5875 mm) flexural strength test pieces. The flexural strength testpieces were post-cured at 200° C. for two hours (7200 s) and then testedon an Instron machine with standard methods (ASTM D-790). The Instronmachine was set at a 1 in. (25.4 mm) span, 0.02 in. per minute (0.00085cm/s) crosshead speed and a 0.5 in. per minute (0.021166 cm/s) chartspeed. The Barcol hardness value is on the 934-1 scale. The results arereported in Table I.

COMPARATIVE EXPERIMENT B

A pair of 12 in.×12 in. (304.8 mm×304.8 mm) woven fiberglass clothpieces were equally impregnated with a solution prepared from 50.0 gramsof Bisphenol A dicyanate of Comparative Experiment A, 100 grams ofchloroform and 0.166 grams of cobalt naphthenate (6.0 percent active).Prepolymerization (B-staging), post-curing, laminate fabrication andmechanical property testing were completed using the method of Example 2to provide a tack-free cloth at room temperature. The laminate thusobtained was rigid, white-colored and semi-transparent. The results arereported in Table I.

                  TABLE I                                                         ______________________________________                                                              Comparative                                                           Example 2                                                                             Experiment B                                            ______________________________________                                        Barcol Hardness 46        42                                                  Flexural Strength,                                                            psi             55.4 × 10.sup.3                                                                   48.5 × 10.sup.3                               kPa              382 × 10.sup.3                                                                    334 × 10.sup.3                               Flexural Modulus,                                                             psi             3.05 × 10.sup.6                                                                   2.93 × 10.sup.6                               kPa             21.0 × 10.sup.6                                                                   20.2 × 10.sup.6                               ______________________________________                                    

EXAMPLE 3 A. Preparation of Unsaturated Diimide

A solution of 1,2-diaminoethane (80.8 grams, 1.34 moles) anddimethylformamide (450 milliliters) was heated to 60° C. with stirringand maintained under a nitrogen atmosphere.Endomethylenetetrahydrophthalic anhydride (441.0 grams, 2.68 moles) wasadded to the reactor over a 90 minute (5400 s) period in 30 to 40 gramaliquots so as to maintain the reaction temperature between 90° and 100°C. After the 90 minute (5400 s) addition time was complete, the reactorwas heated to 110° C. and held for 30 minutes (1800 s). The reactiontemperature was then increased to 155° C. and held for 120 minutes (7200s). After this time no further water was being recovered into the DeanStark trap-cold water condenser assembly, hence the reactor was cooledto room temperature (26° C.). The reaction product was mixed withmethanol and the resulting crystalline product was removed by filtrationand triple-washed with methanol. The white crystals were dried for 12hours (43200 s) at 120° C. under vacuum (50 millimeters Hg) until aconstant product weight of 226 grams (70.4 percent yield) was recovered.Infra-red spectrophotometric analysis and nuclear magnetic resonancespectroscopy confirmed the product structure for the diimide ofendomethylenetetrahydrophthalic anhydride.

B. Preparation of Imide Functional Polyphenol

Phenol (520.0 grams, 5.53 moles) and boron trifluoride etherate (6.0grams) were heated to 110° C. with stirring and maintained under anitrogen atmosphere. A portion of the diimide of endomethylenetetrahydrophthalic anhydride (127.0 grams, 0.361 mole) was added to the reactorand the reaction temperature was increased to 145° C. and held for 180minutes (10800 s), then to 155° C. for 60 minutes (3600 s). After thistime, the excess phenol was vacuum distilled from the reactor (100° C.and 5 millimeter Hg). The product was then powdered and extracted with90° C. water (2 liters). The product was then placed in a 9 inch by 6inch (228.6 mm×152.4 mm) flat glass tray and dried under vacuum (50millimeters Hg) for 16 hours (57600 s) at 120° C. The polyphenol of thediimide of endomethylenetetrahydrophthalic anhydride (209 grams, 99percent yield) was recovered as a light yellow colored, brittle,transparent solid. Infra-red spectrophotometric analysis, nuclearmagnetic resonance spectroscopy and liquid chromatographic analysisconfirmed the product structure.

C. Preparation of Polycyanate of the Imide Functional Polyphenol

A portion of the diimide polyphenol (72.97 grams, 0.1360 mole) dissolvedin chloroform (271.3 milliliters) was added to a reactor and stirredunder a nitrogen atmosphere. The diimide polyphenol-chloroform solutionwas cooled to -5° C. then cyanogen bromide (30.25 grams, 0.2856 mole)was added to the reactor. The stirred solution was allowed toequilibrate at -5° C. then triethylamine (27.66 grams, 0.2734 mole) wasadded to the reactor over a 15-minute (900 s) period and so as tomaintain the reaction temperature at -6° to -2° C. After completion ofthe triethylamine addition, the reaction temperature was maintained at-2° to 5° C. for an additional 30 minutes (1800 s), followed by additionof the reaction product to chilled water (1000 milliliters) withagitation. After 5 minutes (300 s) the water and product mixture wasadded to a separatory funnel and the organic layer recovered. Theorganic layer was washed with 5 percent hydrochloric acid (300milliliters), water (500 milliliters), and then dried over anhydroussodium sulfate. The dry chloroform extract was filtered and solventremoved by rotary evaporation under vacuum. The polycyanate of thepolyphenol of the diimide of endomethylenetetrahydrophthalic anhydridewas recovered (79.8 grams) in 100 percent yield as a light yellowcolored, brittle, transparent solid. Infra-red spectrophotometricanalysis and nuclear magnetic resonance spectroscopy confirmed theproduct structure.

COMPARATIVE EXPERIMENT C Preparation of Bisphenol A Dicyanate

A quantity of 222.45 grams (2.10 moles) of cyanogen bromide was added toa reactor containing 350 milliliters of stirred acetone under a nitrogenatmosphere. The cyanogen bromide-acetone solution was cooled to -5° C.,then 228.30 grams (1.00 mole) of Bisphenol A dissolved in 700milliliters of chilled acetone was added to the reactor. The stirredsolution was allowed to equilibrate at -5° C., then 203.39 grams (2.01moles) of triethylamine was added to the reactor over a 25-minute (1500s) period and so as to maintain the reaction temperature at -5° to 0° C.After completion of the triethylamine addition, the reaction temperaturewas maintained at -6° to 7° C. for an additional 45 minutes (2700 s),followed by addition of the reaction product to chilled water (1 gallon,3.78 liters) with agitation. After 20 minutes (1200 s), the water andproduct mixture was added to a separatory funnel and the resultingslurry of crystals was filtered. The recovered crystalline product wasdissolved in methylene chloride (400 milliliters), washed with 5 percenthydrochloric acid (500 milliliters), washed with water (1000milliliters) and then dried over anhydrous sodium sulfate. The drymethylene chloride solvent was filtered and solvent removed by rotaryevaporation under vacuum. Bisphenol A dicyanate (245.3 grams) wasrecovered in 88.1 percent yield as a light tan colored crystallinesolid. Infra-red spectrophotometric analysis confirmed the productstructure.

EXAMPLE 4

A pair of 12 in.×12 in. (304.8 mm×304.8 mm) woven fiberglass clothpieces were equally impregnated with a solution prepared from 12.5 gramsof the polycyanate diimide of Example 3-C, 37.5 grams Bisphenol Adicyanate of Comparative Experiment C, chloroform (100 grams) and cobaltnaphthenate (0.166 grams, 6.0 percent active).

The fiberglass cloth used was a commercial-grade product treated with aproprietary coupling agent (Burlington 76-28 electrical laminatingcloth) and had an average weight of 0.14 gram per square inch (0.0217g/cm²). The pair of impregnated fiberglass cloths was allowed to dry for24 hours (86400 s) at room temperature (25° C.) followed byprepolymerization (B-staging) in a vented, forced air, convection-typeoven for thirty minutes (1800 s) at 70° C., twenty-three minutes (1380s) at 90° C., 10 minutes (600 s) at 110° C., then fourteen minutes (840s) at 150° C. Each cloth was cooled, found to be tack-free at roomtemperature and then cut to provide eight 6 in.×6 in. (152.4 mm×152.4mm) pieces. The pieces were stacked into a 6 in.×6 in.×1/16 in. (152.4mm×152.4 mm×1.5874 mm) stainless steel frame and placed betweenstainless steel plates which had been coated with a silicone moldrelease. The plates were loaded into a 200° C. hot press (PasadenaHydraulics Inc., Model P-215 ) and maintained for 2 hours (7200 s) at5000 psi (34.5 MPa). After this time, a 6 in.×6 in.×1/16 in. (152.4mm×152.4 mm×1.5875 mm) light yellow-colored, transparent, rigid laminatewas recovered and cut to provide a set of four 1 in.×2 in.×1/16 in.(25.4 mm×50.8 mm×1.5875 mm) flexural strength test pieces. Post-curingand mechanical property testing was completed using the method ofExample 2. The results are reported in Table II.

                  TABLE II                                                        ______________________________________                                                       Example 4                                                      ______________________________________                                        Barcol Hardness  64                                                           Flexural Strength,                                                            psi              72.9 × 10.sup.3                                        kPa               503 × 10.sup.3                                        Flexural Modulus,                                                             psi              2.65 × 10.sup.6                                        kPa              18.3 × 10.sup.6                                        ______________________________________                                    

EXAMPLE 5

A commercial grade of bisphenol A diglycidyl ether (219.60 grams, 0.60mole) having an epoxide equivalent weight (EEW) of 183 was reacted withthe diimide polyphenol (53.65 grams, 0.10 mole) ofendomethylenetetrahydrophthalic anhydride and 1,2-diaminoethane toprovide an advanced epoxy resin with imide functionality. The diimidepolyphenol was prepared using the method of Example 1-A and B scaled up2.1 fold and with the single exception that the t-butanol azeotropicdistillation step was omitted from the workup. The diimide polyphenol,bisphenol A diglycidyl ether and 60 percent aqueousbenzyltrimethylammonium chloride catalyst (0.27 gram) were added to areactor and heated to 120° C. with stirring under a nitrogen atmosphere.After 60 minutes (3600 s) at the 120° C. reaction temperature, thereactor was cooled and the imide functional advanced epoxy resin wasrecovered as a transparent, light amber colored liquid. Epoxidetitration revealed 17.54 percent epoxide in the resin. A portion of theepoxy resin (269.23 grams) was heated to 75° C. then methylene dianiline(54.36 grams) was added and thoroughly mixed in. This solution was usedto prepare a clear, unfilled 1/8 inch (3.175 mm) casting for heatdistortion temperature (264 psi, 1820 MPa), tensile and flexuralstrength, flexural modulus, percent elongation, and Barcol hardness(934-1 scale) determinations. The casting was cured for 2 hours (7200 s)at 75° C. followed by post curing for 2 hours (7200 s) at 125° C., 2hours (7200 s) at 175° C., then 2 hours (7200 s) at 200° C. Mechanicalproperties of tensile (8) and flexural (6) test pieces were determinedusing an Instron machine with standard test methods (ASTM D-638 andD-790). Heat distortion temperature of clear casting test pieces (2) wasdetermined using an Aminco Plastic Deflection Tester (AmericanInstrument Co.) with standard test methods (ASTM D-648 modified). Theresults are reported in Table III.

COMPARATIVE EXPERIMENT D

A commercial grade of bisphenol A diglycidyl ether (292.80 grams, 0.80mole) having an EEW of 183 was reacted with bisphenol A (30.44 grams,0.1333 mole) to provide an advanced epoxy resin. The bisphenol A,bisphenol diglycidyl ether and 60 percent aqueousbenzyltrimethylammonium chloride catalyst (0.32 gram) were added to areactor and heated to 120° C. with stirring under a nitrogen atmosphere.After 60 minutes (3600 s) at the 120° C. reaction temperature, thereactor was cooled and the bisphenol A advanced epoxy resin wasrecovered as a transparent, light yellow colored liquid. Epoxidetitration revealed 17.54 percent epoxide (EEW=245) in the resin.

A portion of the epoxy resin (316.37 grams) was heated to 75° C. thenmethylenedianiline (62.08 grams) was added and thoroughly mixed in. Thissolution was used to prepare a clear, unfilled 1/8 inch (3.175 mm)casting using the method of Example 5. Physical and mechanicalproperties were evaluated using the method of Example 5. The results arereported in Table III.

                  TABLE III                                                       ______________________________________                                                              Comparative                                                           Example 5                                                                             Experiment D                                            ______________________________________                                        Barcol Hardness 46        38                                                  Heat Distortion 140.5/284.9                                                                             139.5/283.1                                         Temperature, °C./°F.                                            Tensile Strength,                                                             psi             10,401    11,269                                              kPa             71,700    77,700                                              Elongation %    2.70      3.51                                                Flexural Strength,                                                            psi             17,353    19,734                                              kPa             120,000   136,000                                             Flexural Modulus,                                                             psi             573,000   420,000                                             kPa             3.95 × 10.sup.6                                                                   2.90 × 10.sup.6                               ______________________________________                                    

EXAMPLE 6

A set of flexural test pieces (3) were prepared from a portion of theclear, unfilled casting of Example 5. Each test piece was numbered andweighed and then placed in a glass rack and immersed in a boiling (100°C.) water bath. After 24 hours (86400 s), the test pieces were removed,blotted dry, weighed and then tested for flexural strength and modulususing the method of Example 5. The results are reported in Table IVwherein the unexposed (0 hr) values are provided for comparison.

COMPARATIVE EXPERIMENT E

A set of flexural test pieces (3) were prepared from a portion of theclear, unfilled casting of Comparative Experiment D. The test pieceswere exposed to boiling water then tested using the method of Example 6.The exposure was simultaneous with that of Example 6. The results arereported in Table V.

                  TABLE IV                                                        ______________________________________                                                       Hours of Exposure to                                                          100° C. Water                                                          0       24                                                     ______________________________________                                        Barcol Hardness  46        33                                                 (% decrease)     --        (28.3)                                             Flexural strength,                                                            psi               17,353   13,623                                             kPa              120,000   93,900                                             (% decrease)     --        (21.5)                                             Flexural Modulus,                                                             psi              573,000   516,000                                            kPa              3.95 × 10.sup.6                                                                   3.56 × 10.sup.6                              (% decrease)     --        (9.95)                                             ______________________________________                                    

                  TABLE V                                                         ______________________________________                                                       Hours of Exposure to                                                          100° C. Water                                                          0       24                                                     ______________________________________                                        Barcol Hardness  38        24                                                 (% decrease)     --        (36.8)                                             Flexural strength,                                                            psi               19,734   10,759                                             kPa              136,000   74,200                                             (% decrease)     --        (45.5)                                             Flexural Modulus,                                                             psi              420,000   397,000                                            kPa              2.90 × 10.sup.6                                                                   2.74 × 10.sup.6                              (% decrease)     --        (5.48)                                             ______________________________________                                    

EXAMPLE 7 A. Preparation of Unsaturated Diimide

A solution of 1,2-diaminoethane (38.75 grams, 0.646 mole) anddimethylformamide (400 milliliters) was heated to 45° C. with stirringand maintained under a nitrogen atmosphere. Tetrahydrophthalic anhydride(196.30 grams, 1.29 moles) was added to the reactor over a 30 minute(1800 s) period after which time the reactor was heated to 90° C. andheld for 30 minutes (1800 s). The reaction temperature was thenincreased to 130° C. and held for 30 minutes (1800 s) followed bydecreasing the reaction temperature to 110° C. After 90 minutes (5400 s)at the 110° C. temperature, no further water was being recovered intothe Dean Stark trap-cold water condenser assembly, hence the reactor wascooled to room temperature (26° C.). The reaction product was mixed withmethanol (400 milliliters) and then chilled in an ice bath. Thecrystalline product was removed by filtration and washed with methanol.The white crystals were dried for 12 hours (43200 s) at 100° C. until aconstant product weight of 133.0 grams (63 percent yield) was recovered.Infra-red spectrophotometric analysis and nuclear magnetic spectroscopyconfirmed the product structure for the diimide of tetrahydrophthalicanhydride.

B. Preparation of Imide Functional Polyphenol

Phenol (360.0 grams, 3.79 moles) and boron trifluoride etherate (2.0grams) were heated to 120° C. with stirring and maintained under anitrogen atmosphere. A portion of the diimide of tetrahydrophthalicanhydride (38.5 grams, 0.25 mole) was added to the reactor and thereaction temperature was increased to 160° C. and held for 8 hours(28800 s). After this time, the excess phenol was vacuum distilled fromthe reactor. The product was placed in a 9 inch by 6 inch (228.6mm×152.4 mm) flat glass tray and dried under vacuum (50 millimeters Hg)for 18 hours (64800 s) at 120° C. The polyphenol of the diimide oftetrahydrophthalic anhydride (75.3 grams, 99 percent yield) wasrecovered as a yellow colored, brittle transparent solid. Infra-redspectrophotometric analysis and nuclear magnetic resonance spectroscopyconfirmed the product structure.

C. Preparation of Polycyanate of the Imide Functional Polyphenol

A portion of the diimide polyphenol (43.9 grams, 0.085 mole) was addedto a reactor containing 170 milliliters of acetone and stirred under anitrogen atmosphere. The diimide polyphenol-acetone solution was cooledto -5° C. then cyanogen bromide (18.91 grams, 0.1785 mole) was added tothe reactor. The stirred solution was allowed to equilibrate at -5° C.then triethylamine (17.29 grams, 0.1708 mole) was added to the reactorover a 10 minute (600 s) period and so as to maintain the reactiontemperature at -5° to 0° C. After completion of the triethylamineaddition, the reaction temperature was maintained at -3° C. to 6° C. foran additional 20 minutes (1200 s), followed by addition of the reactionproduct to chilled water (2000 milliliters) with agitation. After 5minutes (300 s), the water and product mixture was multiply extractedwith methylene chloride. The combined methylene chloride extract waswashed with 5 percent hydrochloric acid (300 milliliters), water (800milliliters) and then dried over anhydrous magnesium sulfate. The drymethylene chloride extract was filtered and solvent removed by rotaryevaporation under vacuum. The polycyanate of the polyphenol of thediimide of tetrahydrophthalic anhydride was recovered (37.91 grams) in78.7 percent yield as a light orange colored, brittle transparent solid.Infra-red spectrophotometric analysis confirmed the product structure.

EXAMPLE 8

A pair of 12 inch×12 inch (304.8 mm×304.8 mm) woven fiberglass clothpieces were equally impregnated with a solution prepared from 29.4 gramsof the polycyanate of the imide functional polyphenol of Example 7-C, apolyepoxide (35.33 grams) chloroform (125 grams) and 0.215 grams ofcobalt naphthenate (6.0 percent active). The polyepoxide had an epoxideequivalent weight (EEW) of 340.5 and was prepared by advancementreaction of bisphenol A diglycidyl ether (EEW=183) (0.40 mole, 146.4grams) with bisphenol A (0.20 mole, 45.66 grams) andbenzyltrimethylammonium chloride catalyst (60 percent aqueous) (0.19gram) at 120° C. for 50 minutes (3000 s). A laminate was prepared usingthe method of Example 4 except that prepolymerization (B-staging) wasperformed for 30 minutes (1800 s) at 70° C., 15 min. (900 s) at 100° C.,and ten minutes (600 s) at 150° C. The resulting laminate was rigid,light yellow-colored and transparent. Post-curing and mechanicalproperty testing was completed using the method of Example 2. Theresults are reported in Table VI.

                  TABLE VI                                                        ______________________________________                                                       Example 8                                                      ______________________________________                                        Barcol Hardness  65                                                           Flexural Strength,                                                            psi              77.7 × 10.sup.3                                        kPa               536 × 10.sup.3                                        Flexural Modulus,                                                             psi              3.67 × 10.sup.6                                        kPa              25.3 × 10.sup.6                                        ______________________________________                                    

EXAMPLE 9

The diimide polyphenol of endomethylenetetrahydrophthalic anhydride and1,2-diaminoethane (81.09 grams, 0.15 mole), epichlorohydrin (138.80grams, 1.50 mole), isopropanol (35 percent by weight of epichlorohydrinused, 74.74 grams), and water (8 percent by weight of epichlorohydrinused, 12.07 grams) were added to a reactor and stirred under a nitrogenatmosphere at 70° C. until a solution was formed. The reactor wasmaintained at 70° C. and dropwise addition of a sodium hydroxide (21.60grams, 0.54 mole) solution in water (86.40 grams) commenced and wascompleted over the next 45 minutes (2700 s). After 20 minutes (1200 s)of further reaction, a second solution of sodium hydroxide (9.60 grams,0.24 mole) in water (38.40 grams) was added dropwise to the reactor overthe next 20 minutes (1200 s). Twenty minutes (1200 s) later, the reactorwas cooled to 50° C. then an initial water wash (600 grams) was added tothe reactor. The reactor contents were transferred to a separatoryfunnel containing additional epichlorohydrin (200 grams). The water washlayer was separated and discarded while the organic layer was added backinto the separatory funnel along with a second water wash (200 grams).The water wash layer was separated and discarded and the recoveredorganic layer was stripped of solvents by rotary evaporation at 100° C.for 60 minutes (3600 s) under vacuum. The epoxy resin was recovered(70.46 grams) as a transparent, light amber-colored, tacky solid at roomtemperature (25° C.). Infra-red spectrophotometric analysis confirmedthe product structure and epoxide titration revealed 11.52 percentepoxide in the product.

EXAMPLE 10 Preparation of Imide Functional Polyphenol Using a 4 to 1Mole Ratio of Phenol to Unsaturated Diimide

Phenol (150.0 grams, 1.67 moles) and boron trifluoride etherate (3.0grams) were heated to 120° C. with stirring and maintained under anitrogen atmosphere. A portion of the diimide ofendomethylenetetrahydrophthalic anhydride (147.0 grams, 0.412 moles)prepared using the method of Example 1-A was added to the reactor andthe reaction temperature was increased to 160° C. and held for 480minutes (28800 s). After this time, the excess phenol was vacuumdistilled from the reactor (100° C. and 5 millimeter Hg). The productwas then placed in a 9 inch by 6 inch (228.6 mm×152.4 mm) flat glasstray and dried under vacuum (50 millimeters Hg) for 72 hours (259200 s)at 100° C. During the vacuum drying, a small amount of unreacted diimidesublimed from the light yellow colored, brittle, transparent solidproduct. Nuclear magnetic resonance spectroscopy demonstrated incompleteconversion of the unsaturation of the unsaturated diimide startingreactant.

EXAMPLE 11

Portions (0.20 gram) of the imide functional polyphenols of Example 3-Band Example 10 were analyzed by size exclusion chromatography. A portion(0.20 gram) of the unsaturated diimide of Example 3-A was analyzed andused as a reference standard. The following results were obtained:

    ______________________________________                                                      Unsaturated                                                                            Diimide                                                              Diimide  Polyphenols                                                          (Area %) (Area %)                                               ______________________________________                                        Example 3-A     100        none                                               (reference standard)                                                          Example 3-B     none       100                                                Example 10      26.4       73.6.sup.1                                         ______________________________________                                         .sup.1 Also includes diimide monophenols present                         

The diimide polyphenols from Example 3-B were further characterized bythe size exclusion chromatographic analysis as containing 75.8 areapercent of the diimide diphenols (Formula I where n¹ =0) and 24.2 areapercent of the diimide polyphenols (Formula I where n¹ =1 to about 10).Minor amounts (less than 5 percent) of norbornyl unsaturation(attributed to compositions of the structure represented by Formula II)were detected by nuclear magnetic resonance spectroscopy in the diimidepolyphenol product of Example 3-B.

EXAMPLE 12

A commercial grade of bisphenol A diglycidyl ether (219.60 grams, 0.60mole) having an epoxide equivalent weight (EEW) of 183 was reacted withthe diimide polyphenol (70.98 grams, 0.132 mole) ofendomethylenetetrahydrophthalic anhydride and 1,2-diaminoethane toprovide an advanced epoxy resin with imide functionality. The diimidepolyphenol was prepared using the method of Example 3-A and 3-B. Thediimide polyphenol, bisphenol A diglycidyl ether and 60 percent aqueousbenzyltrimethylammonium chloride catalyst (0.29 gram) were added to areactor and heated to 120° C. with stirring under a nitrogen atmosphere.After 60 minutes (3600 s) at the 120° C. reaction temperature, thereactor was cooled and the imide functional advanced epoxy resin wasrecovered as a transparent, light amber colored liquid. Epoxidetitration revealed 15.13 percent epoxide in the resin. A portion of theepoxy resin (250.0 grams) was heated to 75° C. then methylene dianiline(43.54 grams) was added and thoroughly mixed in. The resulting solutionwas cured on a glass plate for 2 hours (7200 s) at 75° C. followed bypost curing for 2 hours (7200 s) at 125° C., 2 hours (7200 s) at 175°C., then 2 hours (7200 s) at 200° C. Thermogravimetric analysis (TGA) ofa 13.74 milligram portion of the cured product was performed. Weightloss was recorded as a function of temperature at a 10° C. per minuterate of increase in a stream of nitrogen flowing at 35 cubic centimetersper minute. The results are reported in Table VII.

                  TABLE VII                                                       ______________________________________                                        Weight Loss (%)                                                               100° C.                                                                          300° C.                                                                        350° C.                                                                           400° C.                                                                      450° C.                             ______________________________________                                        0.1       0.8     2.1        24.6  65.0                                       ______________________________________                                    

We claim:
 1. A polyepoxide composition resulting from reacting(A) anyone or a combination of any two or more of the materials represented bythe following formulas (I) and (II) ##STR17## wherein each Q isindependently ##STR18## each R is independently a hydrocarbyl grouphaving from 1 to about 10 carbon atoms, or a ##STR19## group; each A isindependently a divalent hydrocarbyl group having from 1 to about 10,carbon atoms, --S--, --S--S--, --O--, ##STR20## each R' is independentlyhydrogen, chlorine, bromine, a hydrocarbyl or hydrocarbyloxy grouphaving from 1 to about 3 carbon atoms; each R" is hydrogen or ahydrocarbyl group having from 1 to about 3 carbon atoms; Z is a grouprepresented by the formula ##STR21## wherein R" is hydrogen or ahydrocarbyl group having from 1 to about 4 carbon atoms; each x has avalue of zero or 1; each y has a value of zero or 1; each nindependently has an average value from zero to about 20, and n¹ has avalue from zero to about 10; with (B) at least one material representedby the following formulas (VII), (VIII), (IX) or (X) ##STR22## whereineach A is independently a divalent hydrocarbyl group having from 1 toabout 10 carbon atoms, --S--, --S--S--, --O--, ##STR23## each A' isindependently a divalent hydrocarbyl group having from 1 to about 10carbon atoms; each y independently has a value of zero or 1; each R' isindependently hydrogen, chlorine, bromine, a hydrocarbyl orhydrocarbyloxy group having from 1 to about 4 carbon atoms; m' has avalue from 0.001 to about 10; and y has a value of zero or 1;whereincomponents (A) and (B) are employed in quantities which provides aphenolic hydroxyl to epoxide ratio of from about 0.01:1 to about 0.99:1.2. A polyepoxide composition of claim 1 wherein(i) component (A)comprises (1) from about 75 to about 100 percent by weight of a materialrepresented by formula (I) where n¹ has a value of zero and (2) fromabout zero to about 25% by weight of any one or more of the materialsrepresented by formulas (I) and (II) where n¹ has a value from 1 toabout 10; (ii) in component (B), each A and A' is a divalent hydrocarbongroup having from 1 to about 4 carbon atoms, m' has a value from 0.01 toabout 3 and y has a value of 1; and (iii) components (A) and (B) arepresent in quantities which provides a phenolic hydroxyl to epoxideratio of from about 0.05:1 to about 0.3:1.
 3. A polyepoxide compositionof claim 2 wherein(i) in component (A), each R is independently ahydrocarbyl group having from 2 to about 5 carbon atoms; each R' ishydrogen; each n independently has an average value from zero to about 8and n¹ has a value from zero to about 2; and (ii) component (B) isrepresented by formula (VII) wherein each R' is independently hydrogenor bromine.
 4. A polyepoxide composition of claim 3 wherein in component(A) each n has a value of zero.
 5. A polyepoxide composition of claim 4wherein in component (A) each x has a value of zero.
 6. A polyepoxidecomposition of claim 4 wherein in component (A) each x has a value ofone.
 7. A polyepoxide composition of claim 4 wherein component (B) isbisphenol A, tetrabromobisphenol A or a mixture thereof.
 8. Apolyepoxide composition of claim 5 wherein component (B) is bisphenol A,tetrabromobisphenol A or a mixture thereof.
 9. A polyepoxide compositionof claim 6 wherein component (B) is bisphenol A, tetrabromobisphenol Aor a mixture thereof.
 10. A polyepoxide composition resulting fromreacting(A) any one or a combination of any two or more of the materialsrepresented by the following formulas (I) and (II) ##STR24## whereineach Q is independently ##STR25## each R is independently a hydrocarbylgroup having from 1 to about 10 carbon atoms, or a ##STR26## group; eachA is independently a divalent hydrocarbyl group having from 1 to about10, carbon atoms, --S--, --S--S--, --O--, ##STR27## each R' isindependently hydrogen, chlorine, bromine, a hydrocarbyl orhydrocarbyloxy group having from 1 to about 3 carbon atoms; each R" ishydrogen or a hydrocarbyl group having from 1 to about 3 carbon atoms; Zis hydrogen; each x has a value of zero or 1; each y has a value of zeroor 1; each n independently has an average value from zero to about 20,and n¹ has a value from zero to about 10; with (B) at least one materialrepresented by the following formulas (III), (IV), (V) or (VI) ##STR28##wherein each A is independently a divalent hydrocarbyl group having from1 to about 10 carbon atoms, --S--, --S--S--, --O--, ##STR29## each A' isindependently a divalent hydrocarbyl group having from 1 to about 10carbon atoms; each y independently has a value of zero or 1; each R' isindependently hydrogen, chlorine, bromine, a hydrocarbyl orhydrocarbyloxy group having from 1 to about 4 carbon atoms; each R" isindependently hydrogen or a hydrocarbyl group having from 1 to about 4carbon atoms; m has a value from zero to about 40; m' has a value from0.001 to about 10; and y has a value of zero or 1; wherein components(A) and (B) are employed in quantities which provides a phenolichydroxyl to epoxide ratio of from about 0.01:1 to about 0.99:1.
 11. Apolyepoxide composition of claim 10 wherein(i) component (A) comprises(1) from about 75 to about 100 percent by weight of a materialrepresented by formula (I) where n¹ has a value of zero and (2) fromabout zero to about 25% by weight of any one or more of the materialsrepresented by formulas (I) and (II) where n¹ has a value from 1 toabout 10; (ii) in component (B), each A and A' is a divalent hydrocarbongroup having from 1 to about 4 carbon atoms, each R" is hydrogen, m hasa value from zero to about 10, m' has a value from 0.01 to about 3 and yhas a value of 1; and (iii) components (A) and (B) are present inquantities which provides a phenolic hydroxyl to epoxide ratio of fromabout 0.05:1 to about 0.3:1.
 12. A polyepoxide composition of claim 11wherein(i) in component (A), each R is independently a hydrocarbyl grouphaving from 2 to about 5 carbon atoms; each R' is hydrogen; each nindependently has an average value from zero to about 8 and n¹ has avalue from zero to about 2; and (ii) component (B) is represented byformula (III) wherein each R' is independently hydrogen or bromine. 13.A polyepoxide composition of claim 12 wherein in component (A) each nhas a value of zero.
 14. A polyepoxide composition of claim 13 whereinin component (A) each x has a value of zero.
 15. A polyepoxidecomposition of claim 13 wherein in component (A) each x has a value ofone.
 16. A polyepoxide composition of claim 13 wherein component (B) isbisphenol A, tetrabromobisphenol A or a mixture thereof.
 17. Apolyepoxide composition of claim 14 wherein component (B) is bisphenolA, tetrabromobisphenol A or a mixture thereof.
 18. A polyepoxidecomposition of claim 15 wherein component (B) is bisphenol A,tetrabromobisphenol A or a mixture thereof.
 19. A curable compositioncomprising at least one polyepoxide composition of claims 1, 2, 3 4, 5,7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17 or 18 and a curing amount of atleast one curing agent therefor.
 20. A product resulting from curing thecomposition of claim
 19. 21. A product of claim 19 which contains one ormore reinforcing materials.